Chromium Complex Dyes

ABSTRACT

The present invention relates to novel 1:2 chromium complex dyes, processes for their preparation and their use for dyeing or printing fibre materials containing hydroxyl groups or containing nitrogen. 
     The present invention relates to a 1:2 chromium complex dye of formula (I) 
     
       
         
         
             
             
         
       
     
     wherein all substituents are as defined in the claims, a process for their preparation and their use for dyeing or printing fiber materials containing hydroxyl groups or containing nitrogen.

The present invention relates to novel 1:2 chromium complex dyes,processes for their preparation and their use for dyeing or printingfiber materials containing hydroxyl groups or containing nitrogen.

The invention relates to a 1:2 chromium complex dye of formula (I)

wherein

R₁ is H, Cl, Br or NO₂, R₂ is H, Cl, Br, —NO₂, —SO₂NH₂ or —SO₃H

R₃ is O(CH₂)_(n)OR₄ or (CH₂)OR₄,R₄ is H; linear C₁₋₄alkyl; branched C₃₋₄alkyl or —SO₃H,n is 1, 2, 3 or 4 andKa⁺ is a cationas well as mixtures thereof and/or salts thereof.

The linear or branched alkyl groups may be substituted or unsubstituted.Suitable substituents may be for example hydroxyl, halogens, such as Clor Br or a sulpho-group

In preferred compounds according to formula (I) R₄ is H; C₁₋₃alkyl or—SO₃H, and n is 1, 2, 3 or 4, by preference R₄ is H or C₁₋₃alkyl, and nis 1, 2, 3 or 4.

In preferred compounds according to formula (I) R₃ is in the paraposition relative to the nitrogen atom.

In preferred compounds according to formula (I) R₁ signifiesindependently H or NO₂, by preference R₁ signifies NO₂.

In preferred compounds according to formula (I) R₂ signifiesindependently NO₂ or SO₂NH₂, by preference R₂ signifies NO₂.

In more preferred compounds according to formula (I) R₄ is H; CH₃ orCH₂CH₃ and n is 2, 3 or 4.

In more preferred compounds according to formula (I) R₄ is H and n is 2.

Suitable cations K are alkali metal, alkaline earth metal, ammonium,alkanolammonium or alkylammonium cations. K can also be more than onecation, for example as in the case of monovalent cations. Examples ofcorresponding cations are the sodium, lithium or ammonium cations ormono-, di- or triethanolammonium cations.

A further embodiment of the present invention is a process for theproduction of compounds according to formula (I), which comprisesreacting an azo compound of the formula (II)

with a 1:1 chromium complex compound of the formula (III)

in which R₁, R₂, R₃ and R₄ are defined as above.

The reaction of the azo compound of the formula (II) with the 1:1chromium complex compound of the formula (III) is carried out, forexample, in an aqueous medium at a temperature of, for example, 40° C.to 130° C., in particular 70° C. to 100° C., at a pH of, for example, 8to 14, in particular at a pH of 10 to 13. The reaction is advantageouslycarried out in the presence of an agent which neutralizes mineral acidor an alkaline agent, for example in the presence of an alkali metalcarbonate, alkali metal acetate or alkali metal hydroxide, sodium beingpreferred as the alkali metal.

The compounds of the formulae (II) and (III) are known or can beobtained analogously to known processes.

Compounds of the formula (II) can be obtained by customary diazotizationand coupling reactions. The diazotization is as a rule carried out bythe action of nitrous acid in aqueous-mineral acid solution at a lowtemperature, for example 0° C. to 20° C., and the coupling isadvantageously carried out at an alkaline pH, for example at a pH of 8to 12.

1:1 chromium complex compounds of the formula (III) can thus be obtainedin accor-dance with customary chroming processes, in which the reactioncan be carried out with the chromium salt, for example in an aqueousmedium, if appropriate under pressure, at a temperature of, for example,90° C. to 130° C. Chromium salts are, for example, chromium(III)acetate, chromium(III) nitrate, chromium(III) chloride, chromium(III)salicylate or, in particular, chromium(III) sulfate.

A further embodiment of the invention is a process for dyeing orprinting fiber materials containing hydroxyl groups or containingnitrogen.

Fiber materials are preferably either naturally occurring polyamidefiber materials, for example silk or, in particular, wool, or syntheticpolyamide fiber materials, for example polyamide 6 or polyamide 6,6, orwool- or polyamide-containing blend fabric. Synthetic polyamide fibermaterials are of particular interest here.

The above fiber material can be in the most diverse processing forms,for example as fiber, yarn, woven fabric or knitted fabric, and inparticular in the form of carpets.

The dyeing or printing can be carried out in customary dyeing orprinting apparatuses. The dye liquors or printing pastes can comprisefurther additives, for example wetting agents, antifoams, levelingagents or agents which influence the properties of the textile material,for example softening agents, additives for providing a flame-resistantfinish or soil-, water- and oil-repellent agents, as well aswater-softening agents and naturally occurring or synthetic thickeners,for example alginates and cellulose ethers.

In a preferred printing process, the padding method is used, for examplepad-steam, pad-thermofix, pad-dry, pad-batch, pad-jig and pad-roll.Alternatively, printing may be carried out using ink-jet methods.

The 1:2 chromium complex dyes of the formula (I) according to theinvention give level dyeings with good all-round properties. The 1:2chromium complex dyes of the formula (I) according to the invention isalso suitable as a component in a dyeing mixture.

The examples below serve to illustrate the invention. Unless statedotherwise, the percentages are by weight, and the degrees are given inCelsius.

EXAMPLE 1A

195 Parts of4-Hydroxy-7-[(4-(2′-hydroxyethoxy)phenyl)amino]-naphthalene-2-sulfonicacid, solved in 600 parts of water and 45 parts of a 30% sodiumhydroxide solution. Then 50 parts of urea were added at a temperature of25° C. A diazonium salt solution, formed at 0-5° C. and a pH of 1 from amixture of 99.5 parts of 2-Amino-4,6-dinitro-1-hydroxybenzene and 125parts by volume of 4N sodium nitrite solution, is added now within 30minutes. During the coupling reaction the pH is maintained at 9-10 bythe continuous adding of a 30% sodium hydroxide solution. At the end ofthe reaction the product obtained is salted out and filtered by suction.The compound thus obtained having the formula 1

The still damp residue after suction filtration is added to a mixture of4000 parts of water, 65 parts of formic acid and 125 parts ofchromium-(III)-sulfate and stirred as well for 5 hours at a temperatureof 130° C. and a pressure of 2 bar. After reaction is complete the1:1-chromium complex thus formed is isolated by conventional methods andfiltered. The product has the formula 2

EXAMPLE 1B

149.3 parts of the monoazo-compound having formula 3

obtained by conventional methods is suspended in 3000 parts of water at75-80° C. and a pH of 8-9. To this mixture 318 parts of the 1:1 chromiumcomplex having the formula (2)

obtained by the method, described in Example 1a, is added whilestirring. At the same time the pH is kept at 10 by the addition of a 30%sodium hydroxide solution. After reaction is completed the resulting 1:2chromium complex is salted-out using conventional methods, filtered anddried at 60° C. under vacuum. The end product conforms to the formula(4)

and dyes wool and synthetic polyamides to a blue shade. Dyeings thusobtained display excellent light and wet fastness properties.

EXAMPLES 2-15

Table 1 discloses several dyestuffs (substituents according to theformula (5)) which are formed according to the method analogous to thisdescribed in Examples 1a to 1b employing corresponding startingmaterials. In all cases the dyestuff obtained dyes wool and syntheticpolyamides to a blue shade and dyeings thus obtained display excellentlight and wet fastness properties.

TABLE 1 (5)

Example R₁ R₂ R₃  2 —NO₂ —NO₂ —CH₂CH₂OH  3 —NO₂ —SO₂NH₂ —CH₂OH  4 —H—NO₂ —CH₂CH₂CH₂OH  5 —H —NO₂ —CH₂CH₂CH₂CH₂OH  6 —NO₂ —NO₂ —OCH₂CH₂OCH₃ 7 —NO₂ —NO₂ —OCH₂CH₂OCH₂CH₃  8 —NO₂ —SO₂NH₂ —OCH₂CH₂OCH₃  9 —NO₂—SO₂NH₂ —OCH₂CH₂OCH₂CH₃ 10 —NO₂ —NO₂ —OCH₂CH₂OSO₃H 11 —NO₂ —SO₂NH₂—OCH₂CH₂OH 12 —Cl —NO₂ —OCH₂CH₂OH 13 —NO₂ —Cl —OCH₂CH₂OH 14 —H —Cl—OCH₂CH₂OCH₃ 15 —H —NO₂ —OCH₂CH₂OCH₂CH₃

APPLICATION EXAMPLE A

A dyebath at 40° C., consisting of 2000 parts of water, 1 part of aweakly cation-active leveling agent which is based on an ethoxylatedaminopropyl fatty acid amide and which has affinity for dye, 1.5 partsof the dye of Example 1 and adjusted to pH 6 with 0.5 parts of 40%acetic acid is entered with 100 parts of nylon-6 fabric. After 10minutes at 40° C., the dyebath is heated to 98° C. at a rate of 1° C.per minute and then left at the boil for 45-60 minutes. Thereafter it iscooled down to 70° C. over 15 minutes. The dyeing is removed from thebath, rinsed with hot and then with cold water and dried. The resultobtained is a grey polyamide dyeing possessing very high lightfastness.

APPLICATION EXAMPLE B

A dyebath at 40° C., consisting of 4000 parts of water, 1 part of aweakly amphoteric leveling agent which is based on a sulfated,ethoxylated aminopropyl fatty acid amide and which has affinity for dye,2 parts of the dye of Example 1 and adjusted to pH 6 with 0.5 parts of40% acetic acid is entered with 100 parts of wool fabric. After 10minutes at 40° C., the dyebath is heated to boiling at a rate of 1° C.per minute and then left at the boil for 45-60 minutes. Thereafter it iscooled down to 70° C. over 20 minutes. The dyeing is removed from thebath, rinsed with hot and then with cold water and dried. The resultobtained is a grey wool dyeing possessing very high lightfastness.

APPLICATION EXAMPLE C

100 parts of a woven nylon-6 material are padded with a 50° C. liquorconsisting of

40 parts of the dye of Example 1,

100 parts of urea,

20 parts of a nonionic solubilizer based on butyldiglycol,

15-20 parts of acetic acid (to adjust th pH to 4),

10 parts of a weakly cation-active leveling agent which is based on anethoxylated aminopropyl fatty acid amide and has affinity for dye and

810-815 parts of water (to make up to 1000 parts of padding liquor).

The material thus impregnated is rolled up and left to dwell in asteaming chamber under saturated steam conditions at 85-98° C. for 3-6hours for fixation. Then the dyeing is rinsed with hot and cold waterand dried. The result obtained is a grey nylon dyeing having goodlevelness in the piece and good lightfastness.

APPLICATION EXAMPLE D

A textile cut pile sheet composed of nylon-6 and having a synthetic basefabric is padded with a liquor containing per 1000 parts

-   -   2 parts of dye of Example 1    -   4 parts of a commercially available thickener based on carob        flour ether    -   2 parts of a non-ionic ethylene oxide adduct of a higher        alkylphenol    -   1 part of 60% acetic acid.

This is followed by printing with a paste which contains per 1000 partsthe following components:

-   -   20 parts of commercially available alkoxylated fatty alkylamine        (displace product)    -   20 parts of a commercially available thickener based on carbo        fluor ether.

The print is fixed for 6 minutes in saturated steam at 100° C., rinsedand dried. The result obtained is a level-colored cover material havinga grey and white pattern.

1. A 1:2 chromium complex dye of formula (I)

wherein R₁ is H, Cl, Br or NO₂, R₂ is H, Cl, Br, —NO₂, —SO₂NH₂ or —SO₃HR₃ is O(CH₂)_(n)OR₄ or (CH₂)_(n)OR₄, R₄ is H; linear C₁₋₄alkyl; branchedC₃₋₄alkyl or —SO₃H, n is 1, 2, 3 or 4 and Ka⁺ is a cation as well asmixtures thereof and/or salts thereof.
 2. A 1:2 chromium complex dye offormula (I) according to claim 1, wherein R₃ is in the para positionrelative to the nitrogen atom and R₄ is H; CH₃ or CH₂CH₃ and n is 2, 3or 4, as well as mixtures thereof and/or salts thereof.
 3. A 1:2chromium complex dye of formula (I) according to claim 1, wherein R₁ isH or NO₂ and R₂ is NO₂ or SO₂NH₂.
 4. A process for the production ofcompounds of formula (I) according to claim 1 comprising the step ofreacting an azo compound of the formula (II)

with a 1:1 chromium complex compound of the formula (III)

wherein R₁, R₂, R₃ and R₄ are defined above.
 5. An ink-jet inkcomprising at least one dyestuff according to claim
 1. 6. A process fordyeing or printing a fiber material containing hydroxyl groups ornitrogen groups comprising the step of contacting the fiber materialwith at least one dyestuff according to formula (I), its salts ormixtures thereof.
 7. A fiber material containing hydroxyl groups ornitrogen groups dyed or printed with at least one compound as defined inclaim 1 its salts or mixtures thereof.
 8. A process for the preparationof an ink-jet ink comprising the step of mixing at least one dyestuffaccording to claim 1 with at least one additional ink-jet inkformulation compound.